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US4636264A - Autodeposition post-bath rinse process - Google Patents

Autodeposition post-bath rinse process Download PDF

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Publication number
US4636264A
US4636264A US06/802,635 US80263585A US4636264A US 4636264 A US4636264 A US 4636264A US 80263585 A US80263585 A US 80263585A US 4636264 A US4636264 A US 4636264A
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US
United States
Prior art keywords
rinse
salt
resin
aqueous solution
chromate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/802,635
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English (en)
Inventor
Lutz Schellenberg
Matthias Hamacher
Ronald Broadbent
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gerhard Collardin GmbH
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Gerhard Collardin GmbH
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Filing date
Publication date
Application filed by Gerhard Collardin GmbH filed Critical Gerhard Collardin GmbH
Assigned to GERHARD COLLARDIN GMBH, A CORP. OF GERMANY reassignment GERHARD COLLARDIN GMBH, A CORP. OF GERMANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BROADBENT, RONALD, HAMACHER, MATTHIAS, SCHELLENBERG, LUTZ
Application granted granted Critical
Publication of US4636264A publication Critical patent/US4636264A/en
Anticipated expiration legal-status Critical
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
    • B05D7/144—After-treatment of auto-deposited coatings

Definitions

  • This invention relates to improving the anticorrosive properties of an autodeposition coating by a post-bath rinse which introduces certain metal salts into the resin coating.
  • Inorganic pigments i.e. insoluble colored substances
  • U.S. Pat. No. 4,030,945 discloses a process wherein metal surfaces, after they are autodeposition coated with organic resins, are rinsed with diluted aqueous solutions containing hexavalent chromium or combinations of hexavalent chromium with formaldehyde-reduced chromium compounds.
  • chromium compounds such as chromium trioxide (chromic acid), and/or water or acid soluble chromates or dichromates can be employed, especially potassium or sodium dichromate, or sodium, potassium, or lithium chromate.
  • U.S. Pat. No. 3,647,567 discloses what appear to be autodeposited resin coatings which are subjected to a post-bath rinse using chromium trioxide, phosphoric acid, or water soluble or acid soluble chromates and dichromates.
  • the specifically disclosed chromates or dichromates are: potassium, sodium, ammonium, calcium, cesium, lithium, magnesium, zinc, etc. (sic) chromates and sodium, ammonium, lithium, etc. (sic) dichromates, zinc chromate being preferred.
  • a zinc "chromate" containing solution was prepared by adding an excess of zinc carbonate to a 10% aqueous chromium oxide solution.
  • the activating systems are oxidizing acid systems, specifically nitric acid or sulfuric acid when the substrate contains iron, zinc, or tin.
  • a mixture of fluoroboric acid, hydrofluoric acid, chromic anhydride and potassium ferricyanide can also be employed as the activating system.
  • inorganic pigments improving the autodeposition coating anticorrosive property directly into the coating bath and deposit same along with the organic resin layer on the metal surface.
  • Known anticorrosive pigments include compounds of barium, strontium, zinc and lead, the chromates of said metals being preferably used. Such chromates without exception are only sparingly soluble in water.
  • the autodeposition method is such that the acidic latex superficially mordants the metal surface to be coated, thereby dissolving metal ions of the metal surface into the solution.
  • Such positive charge carriers cause the stabilized resin dispersion to coagulate in the proximity of the metal surface, whereby a homogeneous coating with the organic resin is effected without electricity. Due to the low pH of this coating process (between 1.5 and 4.0) such anticorrosive pigments are more or less rapidly converted into a soluble form, and theoretically should then be deposited simultaneously with the organic resin particles.
  • the metal cations present in the acidic aqueous solutions contribute to an increased coagulation of the resin dispersion which may even result in a breakdown of the latex due to its complete coagulation.
  • the present invention relates to a process for improving the anticorrosive properties of autodeposited resin coatings on metal substrates which are mechanically and/or chemically cleaned by means of known procedures, autodeposition coated with any optional organic resin and, if desired, rinsed with water, and then
  • Metal substrates which can be better protected against corrosion by application of the process of this invention comprise iron, tin, nickel, lead, chromium, zinc, aluminum, or alloys thereof, especially steel, as well as surfaces which have been coated with one of said metals or its alloys.
  • the organic resins to be autophoretically deposited on the metal surfaces may include a variety of resin materials in latex form as known from numerous publications.
  • examples of such organic coating-forming resin materials are polyethylene, polyacrylates, styrene/butadiene-copolymers, vinyl chloride/vinylidene chloride-copolymers and the like.
  • any autodepositable resin can be used in this invention, those which produce relatively soft coatings, such as acrylic and styrene-butadiene polymers are most improved in their anticorrosive properties by the process of the invention.
  • the polymers are autodeposited according to known methods on metal surfaces which have been chemically and/or mechanically cleaned in the conventional manner.
  • the uncured coatings may be rinsed with water immediately after the actual coating reaction.
  • any of the earlier mentioned metal cations are useful, although lead or nickel salts are preferred.
  • the anions that are useful must form salts which are readily soluble in water with the corresponding cations. Moreover, they must not in any way adversely affect the finished product.
  • salts of the hydrogen halide acids or of sulfuric acid are not suitable for the invention, as their anions, e.g. Cl - and SO 4 2- , are known to corrode metal surfaces and, thus, the solutions thereof will not serve to increase, but rather to reduce, the corrosion resistance of the metal substrate.
  • Salts of the earlier mentioned metals formed with anions of organic carboxylic acids have proven to be particularly valuable for use in the inventive process.
  • acetates (ethanoates), propionates (propanoates), as well as salts of higher carboxylic or dicarboxylic acids can be employed.
  • the acetates of these metals are particularly preferred, as it can be assumed that these anions are decomposed to form CO 2 and H 2 O when the autodeposited coating is cured in the presence of hexavalent chromium ions. Such decomposition products will not negatively influence the anticorrosive propeties imparted to the metal surfaces.
  • the amount of the metal salts in the aqueous rinse solutions with which the autodeposited uncured-resin coated metal substrates are treated according to this invention may vary within wide limits.
  • the salts of the first rinse are minimally used in an effective amount sufficient to provide an enhancement of the anticorrosive properties of the autodeposited resin after these salts are converted by the second rinse and the resin is cured.
  • the chromates of the second rinse are minimally used in an effective amount sufficient to convert enough of those salts remaining in the resin after the first bath to water insoluble chromate salts which remain in the resin after curing, to provide the enhanced anticorrosive properties.
  • For the first rinse preferably 1 to 10 grams/liter, most preferably 2.5 to 7 grams/liter, of salts as measured by their cations are employed.
  • the pH value of the first rinse can be lowered within the above mentioned pH range of 4.5 to 8.5 using the acid which provides the employed salt's anion.
  • solutions containing lead acetate or nickel acetate may be adjusted with acetic acid to a pH of 4.9 to 5.3.
  • the metal substrates autodeposition coated with the uncured organic resin as described above are contacted with the first rinse salt solutions according to known methods.
  • the coated metal substrates are immersed in the metal salt solutions, spray-treated with these solutions, or treated by a combined dip/spray-procedure.
  • the duration of treatment is 30 to 120 seconds, and preferably about 90 seconds.
  • the salt solutions are at a temperature of 4° C. to 50° C., 20° C. being preferred.
  • the salts are incorporated in the still soft organic resin layer. However, they are still accessible to further chemical reactions and, according to the invention, are treated in a subsequent step with an aqueous chromium-containing second rinse solution, as a result of which the respective organic metal salts are converted into the corresponding chromates.
  • the second rinse aqueous solution required for the step of converting the water-soluble metal salts into the corresponding chromates contains water-soluble hexavalent chromium compounds.
  • examples of such compounds are chromic acid, potassium dichromate, magnesium dichromate, potassium chromate and sodium chromate.
  • any chromium-containing compound which forms hexavalent chromium ions in an acidic aqueous medium can be employed.
  • Preferred hexavalent chromium sources are dichromates, for example calcium dichromate.
  • Such solutions may also be prepared by adding a suitable salt, e.g. calcium carbonate, to an aqueous solution of chromic acid.
  • Solutions which contain trivalent chromium in addition to hexavalent chromium are preferred to be used. Such solutions may also be prepared according to prior art by partially reducing solutions containing hexavalent chromium with suitable reducing agents.
  • One known route comprises adding formaldehyde to a chromic acid solution to reduce part of the hexavalent chromium to trivalent chromium.
  • the mol ratio of trivalent to hexavalent chromium in such solutions is 0.3-3:1. In total the solutions contain 1 to 20, preferably 5 to 15 grams/liter of chromium.
  • the conversion of the metal salts incorporated in the uncured organic resin layer during the first rinse is also effected in accordance with known methods.
  • the metal surfaces can either be immersed in the chromium containing aqueous salt solutions, spray-treated with these solutions, or treated by a combined dip/spray-procedure.
  • the duration of treatment is 30 to 120 seconds preferably about 90 seconds, at a temperature of 4° C. to 50° C., preferably about 20° C.
  • the metal surfaces having been autodeposition coated with an uncured organic resin and then additionally protected against corrosion by the in situ formation of an (insoluble) metal chromate are subsequently cured in any known manner, for example by heating (preferably baking) to elevated temperatures of 90° C. to 150° C., preferably 110° C.
  • the selection of the particular temperature will depend on the type of organic resin used for the coating.
  • a completely continuous autodeposited organic resin surface is formed which, due to its content of incorporated metal chromate, substantially better protects the metal substrate against corrosion than those metal substrates having an autodeposited organic resin layer thereon which has not been autodeposition post-bath rinsed at all or which has been post-bath rinsed only with chromic acid.
  • Test sheets made of a steel material No. 1.1405 [according to German Industrial Norm (DIN); an unalloyed steel, cold-rolled, deep-draw grade; this material is used for body sheets in the automotive industry], after cleaning (1) were coated in an autodeposition coating bath having the following composition, at 20° C. ⁇ 2° C. for 90 seconds:
  • test sheets were subsequently (2) rinsed in water for 30 to 60 seconds, then (3) immersed in the respective metal salt solution as set forth in the following Table 1 at 20° C. for 90 seconds and thereafter (4) rinsed at 20° C. in a solution containing 6.15 g/l trivalent chromium(III) and 10.9 g/l hexavalent chromium(VI) for 90 seconds. Finally, (5) the test sheets were baked in an oven at 110° C. for 30 minutes. Examples 15 and 16 are for comparison.
  • test sheets were subjected to tests of anticorrosive properties according to DIN 53,167 and to Volkswagen(VW) Testing Standard No. 3.17.1 of Jan. 6, 1981 (Test Simulating the Action of Crushed Rock - Salt Spray Test; "Steintsch-Salzspruehtest”).
  • the test sheets were subjected to the test conditions for 240 hours and 480 hours, respectively and evaluated after a recovery period of 1 hour.
  • Q-panels were processed through a 10% by weight solids of a 97.43% by weight styrene-butadiene latex autodepostion bath with 5% by volume of an activator comprising HF and ferric fluoride, and an aqueous carbon black pigment dispersion.
  • the panels were subsequently first rinsed with an aqueous solution of ferrous gluconate (4.6 g/l) followed by a second rinse with aqueous chromic acid which was partially reduced by 37% formaldehyde (3% by weight).
  • the rinsed, uncured autodeposited resin coating was then cured by baking at 160° C. The times for the above were: autodeposition bath--1 min; dwell--1 min; first rinse--1 min; dwell--30 sec; second rinse--1 min; cure--15 min.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Detergent Compositions (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)
US06/802,635 1985-01-09 1985-11-26 Autodeposition post-bath rinse process Expired - Fee Related US4636264A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853500443 DE3500443A1 (de) 1985-01-09 1985-01-09 Verfahren zur verbesserung des korrosionsschutzes autophoretisch abgeschiedener harzschichten auf metalloberflaechen
DE3500443 1985-01-09

Publications (1)

Publication Number Publication Date
US4636264A true US4636264A (en) 1987-01-13

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US06/802,635 Expired - Fee Related US4636264A (en) 1985-01-09 1985-11-26 Autodeposition post-bath rinse process

Country Status (8)

Country Link
US (1) US4636264A (pt)
EP (1) EP0187917B1 (pt)
JP (1) JPS61174973A (pt)
CN (1) CN1008527B (pt)
AT (1) ATE39502T1 (pt)
BR (1) BR8600052A (pt)
CA (1) CA1245918A (pt)
DE (2) DE3500443A1 (pt)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4931317A (en) * 1988-03-30 1990-06-05 Nihon Parkerizing Co., Ltd. Composition and process for the formation of a black coating on surfaces of materials
AU648452B2 (en) * 1991-12-24 1994-04-21 Pont-A-Mousson S.A. Multilayer coating, with manufacturing process and mode of application
WO1994015719A1 (en) * 1992-12-30 1994-07-21 Henkel Corporation Method for applying autodeposition coating
US5372853A (en) * 1993-08-05 1994-12-13 Henkel Corporation Treatment to improve corrosion resistance of autodeposited coatings of metallic surfaces
US5441773A (en) * 1992-01-21 1995-08-15 Betz Laboratories, Inc. Composition and method of forming a black no-rinse conversion coating on metal surfaces
US5470613A (en) * 1992-01-21 1995-11-28 Betz Laboratories, Inc. Composition and method of forming a black no-rinse conversion coating on metal surfaces
US5667845A (en) * 1993-08-05 1997-09-16 Henkel Corporation Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces
US5704995A (en) * 1996-07-16 1998-01-06 Globe Motors, A Division Of Labinal Components And Systems, Inc. Method for forming a black, adherent coating on a metal substrate
US5786030A (en) * 1996-11-12 1998-07-28 Henkel Corporation Spotting resistant gloss enhancement of autodeposition coating
WO2000071265A1 (en) 1999-05-21 2000-11-30 Henkel Corporation Autodeposition post-bath rinse process
US20020011309A1 (en) * 2000-02-18 2002-01-31 Agarwal Rajat K. Rubber-metal Composites
US20030104212A1 (en) * 1999-05-26 2003-06-05 Agarwal Rajat K. Epoxy resin-based autodeposition coatings
US20030149169A1 (en) * 2001-11-14 2003-08-07 Bammel Brian D. Novel epoxy dispersions for use in coatings
US6613387B2 (en) 2000-11-22 2003-09-02 Henkel Corporation Protective reaction rinse for autodeposition coatings
US20040043155A1 (en) * 2002-07-15 2004-03-04 Mcgee John D. Corrosion resistant films based on ethylenically unsaturated monomer modified epoxy emulsions
US20050065242A1 (en) * 2002-07-15 2005-03-24 Henkel Corporation Coatings with enhanced water-barrier and anti-corrosive properties
DE102009029334A1 (de) * 2009-09-10 2011-03-24 Henkel Ag & Co. Kgaa Zweistufiges Verfahren zur korrosionsschützenden Behandlung von Metalloberflächen
WO2012087813A2 (en) 2010-12-20 2012-06-28 Henkel Ag & Co. Kgaa Glossy improved appearance auto-deposition coating, and methods of applying same
WO2014151311A1 (en) 2013-03-15 2014-09-25 Henkel Ag & Co. Kgaa Electrodeposition of an autodepositable polymer
US9228109B2 (en) 2010-12-20 2016-01-05 Henkel Ag & Co. Kgaa Glossy improved appearance auto-deposition coating, and methods of applying same
WO2017117169A1 (en) 2015-12-31 2017-07-06 Henkel Ag & Co. Kgaa Low bake autodeposition coatings
US10323314B2 (en) 2011-06-17 2019-06-18 Henkel Ag & Co. Kgaa Single bath autodeposition coating for combination metal substrates and methods therefor

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3442985A1 (de) * 1984-11-26 1986-05-28 Henkel KGaA, 4000 Düsseldorf Verfahren zur verbesserung des korrosionsschutzes von autophoretisch abgeschiedenen harzueberzuegen auf metalloberflaechen
JP3515183B2 (ja) * 1994-08-30 2004-04-05 臼井国際産業株式会社 金属管における耐食性樹脂被覆構造

Citations (6)

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US3647567A (en) * 1969-11-28 1972-03-07 Celanese Coatings Co Post-dipping of acidic deposition coatings
US3791431A (en) * 1966-06-01 1974-02-12 Amchem Prod Process for coating metals
US4030945A (en) * 1966-06-01 1977-06-21 Amchem Products, Inc. Rinsing coated metallic surfaces
US4186226A (en) * 1978-06-21 1980-01-29 Union Carbide Corporation Autodeposited coatings with increased surface slip
US4186219A (en) * 1975-08-29 1980-01-29 Union Carbide Corporation Maintaining the effectiveness of a coating composition
US4414350A (en) * 1979-09-27 1983-11-08 Amchem Products, Inc. Ferrous complexing agent for autodeposition

Family Cites Families (2)

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CA1089155A (en) * 1975-08-29 1980-11-11 Wilbur S. Hall Treating autodeposited coatings with cr composition
US4411865A (en) * 1979-04-05 1983-10-25 Betz Laboratories, Inc. Method of corrosion inhibition in aqueous mediums

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3791431A (en) * 1966-06-01 1974-02-12 Amchem Prod Process for coating metals
US4030945A (en) * 1966-06-01 1977-06-21 Amchem Products, Inc. Rinsing coated metallic surfaces
US3647567A (en) * 1969-11-28 1972-03-07 Celanese Coatings Co Post-dipping of acidic deposition coatings
US4186219A (en) * 1975-08-29 1980-01-29 Union Carbide Corporation Maintaining the effectiveness of a coating composition
US4186226A (en) * 1978-06-21 1980-01-29 Union Carbide Corporation Autodeposited coatings with increased surface slip
US4414350A (en) * 1979-09-27 1983-11-08 Amchem Products, Inc. Ferrous complexing agent for autodeposition

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU610370B2 (en) * 1988-03-30 1991-05-16 Nihon Parkerizing Company Limited Composition and process for the formation of a black coating on surfaces of materials
US4931317A (en) * 1988-03-30 1990-06-05 Nihon Parkerizing Co., Ltd. Composition and process for the formation of a black coating on surfaces of materials
AU648452B2 (en) * 1991-12-24 1994-04-21 Pont-A-Mousson S.A. Multilayer coating, with manufacturing process and mode of application
US5356679A (en) * 1991-12-24 1994-10-18 Pont-A-Mousson S.A. Pipe surface coating with conversion and thermosetting resin layer, and process for the coating application
US5441773A (en) * 1992-01-21 1995-08-15 Betz Laboratories, Inc. Composition and method of forming a black no-rinse conversion coating on metal surfaces
US5470613A (en) * 1992-01-21 1995-11-28 Betz Laboratories, Inc. Composition and method of forming a black no-rinse conversion coating on metal surfaces
US5385758A (en) * 1992-12-30 1995-01-31 Henkel Corporation Method for applying autodeposition coating
WO1994015719A1 (en) * 1992-12-30 1994-07-21 Henkel Corporation Method for applying autodeposition coating
US5372853A (en) * 1993-08-05 1994-12-13 Henkel Corporation Treatment to improve corrosion resistance of autodeposited coatings of metallic surfaces
US5667845A (en) * 1993-08-05 1997-09-16 Henkel Corporation Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces
US5704995A (en) * 1996-07-16 1998-01-06 Globe Motors, A Division Of Labinal Components And Systems, Inc. Method for forming a black, adherent coating on a metal substrate
US5931993A (en) * 1996-07-16 1999-08-03 Globe Motors Composition for forming a black, adherent coating on a metal substrate
US5786030A (en) * 1996-11-12 1998-07-28 Henkel Corporation Spotting resistant gloss enhancement of autodeposition coating
US6410092B1 (en) * 1999-05-21 2002-06-25 Henkel Corporation Autodeposition post-bath rinse process
WO2000071265A1 (en) 1999-05-21 2000-11-30 Henkel Corporation Autodeposition post-bath rinse process
US20030104212A1 (en) * 1999-05-26 2003-06-05 Agarwal Rajat K. Epoxy resin-based autodeposition coatings
US6833398B2 (en) * 1999-05-26 2004-12-21 Henkel Kommanditgesellschaft Auf Aktien Epoxy resin-based autodeposition coatings
US20020011309A1 (en) * 2000-02-18 2002-01-31 Agarwal Rajat K. Rubber-metal Composites
US6805768B2 (en) 2000-02-18 2004-10-19 Henkel Kommanditgesellschaft Auf Aktien Method of forming rubber-metal composites
US6613387B2 (en) 2000-11-22 2003-09-02 Henkel Corporation Protective reaction rinse for autodeposition coatings
US6989411B2 (en) 2001-11-14 2006-01-24 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Epoxy dispersions for use in coatings
US20030149169A1 (en) * 2001-11-14 2003-08-07 Bammel Brian D. Novel epoxy dispersions for use in coatings
US7138444B2 (en) 2002-07-15 2006-11-21 Henkel Kommanditgesellschaft Auf Atkien (Henkel Kgaa) Corrosion resistant films based on ethylenically unsaturated monomer modified epoxy emulsions
US20050065242A1 (en) * 2002-07-15 2005-03-24 Henkel Corporation Coatings with enhanced water-barrier and anti-corrosive properties
US20040043155A1 (en) * 2002-07-15 2004-03-04 Mcgee John D. Corrosion resistant films based on ethylenically unsaturated monomer modified epoxy emulsions
US7388044B2 (en) 2002-07-15 2008-06-17 Henkel Kommanditgesellschaft Auf Aktien Coatings with enhanced water-barrier and anti-corrosive properties
DE102009029334A1 (de) * 2009-09-10 2011-03-24 Henkel Ag & Co. Kgaa Zweistufiges Verfahren zur korrosionsschützenden Behandlung von Metalloberflächen
US9403188B2 (en) 2009-09-10 2016-08-02 Henkel Ag & Co. Kgaa Two-stage method for the corrosion protection treatment of metal surfaces
WO2012087813A2 (en) 2010-12-20 2012-06-28 Henkel Ag & Co. Kgaa Glossy improved appearance auto-deposition coating, and methods of applying same
US9228109B2 (en) 2010-12-20 2016-01-05 Henkel Ag & Co. Kgaa Glossy improved appearance auto-deposition coating, and methods of applying same
US10323314B2 (en) 2011-06-17 2019-06-18 Henkel Ag & Co. Kgaa Single bath autodeposition coating for combination metal substrates and methods therefor
WO2014151311A1 (en) 2013-03-15 2014-09-25 Henkel Ag & Co. Kgaa Electrodeposition of an autodepositable polymer
US9115442B2 (en) 2013-03-15 2015-08-25 Henkel Ag & Co. Kgaa Electrodeposition of an autodepositable polymer
WO2017117169A1 (en) 2015-12-31 2017-07-06 Henkel Ag & Co. Kgaa Low bake autodeposition coatings
US11426762B2 (en) 2015-12-31 2022-08-30 Henkel Ag & Co. Kgaa Low bake autodeposition coatings

Also Published As

Publication number Publication date
CN1008527B (zh) 1990-06-27
JPS61174973A (ja) 1986-08-06
CN86100013A (zh) 1986-07-09
ATE39502T1 (de) 1989-01-15
CA1245918A (en) 1988-12-06
DE3500443A1 (de) 1986-09-11
EP0187917A1 (de) 1986-07-23
EP0187917B1 (de) 1988-12-28
DE3567035D1 (en) 1989-02-02
BR8600052A (pt) 1986-09-23

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